Stimulus-responsive dynamic liquid crystal elastomers

ABSTRACT

Compositions, systems and methods for use in monitoring an environment or a formation. The compositions can include electrically conductive material that can be used as a sensor. The sensor can have a non-writeable, writeable, and stimulated state. A first signal is used to induce the non-writeable material into a writeable state. In the writeable state, the electrically conductive material has the capacity for actuation in response to an orthogonal signal. In response to the orthogonal signal, the electrically conductive material then undergoes a conformation or shape change. The conformational or shape change induces a strain or actuation that can be used to generate a signal. The stimulated state can be reversible, and in the absence of the orthogonal signal the electrically conductive material may resume its original shape or conformation.

CLAIM OF PRIORITY

This application claims priority to U.S. Provisional Application Ser.No. 63/076,055, filed on Sep. 9, 2020, the entire contents of which ishereby incorporated by reference.

TECHNICAL FIELD

This document relates to compositions and methods of stimulus responsivedynamic liquid crystal elastomers.

BACKGROUND

Liquid crystals are semi-ordered molecules that display long range orderin their liquid crystalline phases. Liquid crystals can be influenced bytheir surrounding environment, and the properties of liquid crystals candepend on their relative shape and orientation.

SUMMARY

This disclosure describes compositions and methods of use ofstimulus-responsive dynamic liquid crystal elastomers. In someimplementations, a composition contains an electrically conductivematerial. The electrically conductive material can be configured torespond to a first signal and enter a writeable state. The electricallyconductive material can be configured to respond to an orthogonal signalto enter a stimulated state.

In some implementations, a composition is provided that includes anelectrically conductive material. The electrically conductive materialis configured to respond to a first signal to enter a writeable state,and to respond to an orthogonal signal to enter a stimulated state. Insome implementations, the electrically conductive material includes afunctionalized liquid crystal elastomer, a signal generating element,and a signal receiving element.

Some implementations provide a system that includes a functionalizedliquid crystal elastomer, a signal generating element, and a signalreceiving element. The functionalized liquid crystal elastomer isconfigured to crosslink in response to a first signal to generate acrosslinked functionalized liquid crystal elastomer. The crosslinkedfunctionalized liquid crystal elastomer is configured to induce a strainin or actuate the signal generating element in response to an orthogonalsignal, wherein inducing the strain in or actuating the signalgenerating element induces the signal generating element to generate areadout signal. The signal receiving element is configured to receivethe signal.

In some implementations, a method is provided for monitoring anenvironment or a formation. The method includes placing a sensor in theenvironment or formation. The sensor can include a functionalized liquidcrystal elastomer. The sensor can include a signal generating element.The method can include providing a first signal to the sensor. Inresponse to the first signal, the functionalized liquid crystalelastomer reacts in a crosslinking reaction to generate a crosslinkedfunctionalized liquid crystal elastomer. The method can include exposingthe sensor to an orthogonal signal. In response to the orthogonalsignal, the crosslinked functionalized liquid crystal elastomer caninduce a strain in or actuate the signal generating element. Inducingstrain in or actuating the signal generating element induces the signalgenerating element to generate a readout signal.

The details of one or more implementations of the disclosure are setforth in the accompanying drawings and the description that follows.Other features, objects, and advantages of the disclosure will beapparent from the description and drawings, and from the claims.

DESCRIPTION OF DRAWINGS

FIG. 1 is an example reaction of RM82 with methylcoumarin to yieldmethylcoumarin-functionalized RM82.

FIG. 2A is an example reaction of RM82 with methylthioanthracene toyield anthracene-functionalized RM82.

FIG. 2B is an example of functionalized RM82 that is the reactionproduct of the reaction between EDDET, RM82, and methylthioanthracene ina 1:2:2 molar ratio.

FIG. 3 is an example of a method 300 for monitoring an environment orformation using a functionalized liquid crystal elastomer sensor.

Like reference symbols in the various drawings indicate like elements.

DETAILED DESCRIPTION

Liquid crystals (LCs) are materials which display long-range order intheir liquid crystalline phases which, depending on their constitutionsand environmental conditions, may respond to various applied stimulisuch as heat, shear field, electric field, magnetic field, and light(ultraviolet, visible, or near-infrared). These external stimuli caninfluence and instruct molecular ordering. In certain LCs, theseresponses have been observed macroscopically through changes in thepolarization of light penetrating the materials, modified shearresponse, and macroscopic material shape change. Liquid crystallineelastomers (LCEs) are polymeric liquid crystals that can be made toretain their liquid crystalline order through cross-linking in theliquid crystalline and aligned state. Artificial material systems ofLCEs can emulate motion and the force output of, for example, naturalmusculo-skeletal systems. LCEs can be programmed pixel-by-pixel withmicron-scale resolution to change specifically in shape in response to athermal stimulus. This class of dynamic materials represents new avenuesof research due their muscle-like contractile forces observed duringshape-change.

Reference will now be made in detail to certain embodiments of thedisclosed subject matter, examples of which are illustrated in part inthe accompanying drawings. While the disclosed subject matter will bedescribed in conjunction with the enumerated claims, it will beunderstood that the exemplified subject matter is not intended to limitthe claims to the disclosed subject matter.

Provided in this disclosure, in part, are compositions ofstimulus-responsive dynamic liquid crystal elastomers and method ofusing the same. An electrically conductive material can be used as asensor, for example, by having a non-writeable, writeable, andstimulated state. A first signal is used to induce the non-writeablematerial into a writeable state. In the writeable state, theelectrically conductive material has the capacity for actuation inresponse to an orthogonal signal. In response to the orthogonal signal,the electrically conductive material then undergoes a conformation orshape change. This is the stimulated state of the material. Theconformational or shape change induces a strain or actuation that can beused to generate a signal. The electrically conductive material caninclude a response material. The response material can be configured topropagate a readout signal in response to the strain or actuation in theelectrically conductive material. The response material can also actuatein response to the actuation of the electrically conductive material.The stimulated state can be reversible, and in the absence of theorthogonal signal the electrically conductive material may resume itsoriginal shape or conformation.

The writeable state is reversible. In the writeable state, a secondsignal can be used to revert the writeable material into a non-writeablestate. Accordingly, the material is reversibly switchable to an “on” orwriteable state and an “off” or non-writeable state.

The electrically conductive material can be a liquid crystal elastomeror mesogen that is functionalized so that the ends of the materialdisplay dynamic functionality, for example by being capable ofreversible crosslinking. The dynamic mesogen can be switched into thewriteable state by a first signal. The first signal can inducecrosslinking of the mesogens, resulting in a crosslinked mesogen that isin the writeable state. Subsequent exposure to an orthogonal stimuluscan result in a stimulated state and conformational or shape change inthe crosslinked mesogen. The crosslinked mesogen can return to thenon-writeable state by exposure to the second signal.

The first and second signal can be light. The primary and secondarystimuli can each have a unique wavelength. For example, the first signalcan be light with a wavelength of 365 nm. The second signal can be alight with a wavelength of 254 nm.

The orthogonal stimulus can be an electric field, a magnetic field,light, heat, or a chemical, metabolite, or both. The orthogonal stimuluscan be a change in an electric field, magnetic field, light, heat, or achange in the concentration of a chemical, metabolite, or both.

The response to orthogonal stimuli can be enhanced using sensitizers.For example, if electric field responsivity is sought, an electric fieldsensitizer may be added to or dispersed into the electrically conductivematerial. Electric field sensitizers can include, for example, carbonblack, carbon nanotubes, carbon nanofiber, or carbon fiber. If theorthogonal stimulus is light, a chromophoric sensitizer can be added toor dispersed into the electrically conductive material. Chromophoricsensitizers include, for example, titania nanoparticles, n-doped titaniananoparticles, p-doped titania nanoparticles, porphyrins, expandedporphyrins, and conjugated polymers. Conjugated polymers can include,for example, polythiophene, polyaniline, polyphenylene vinylene andderivatives. Chromophoric sensitizers can include, for example,rhodamine dyes or fluorescein dyes.

In some implementations, the liquid crystal elastomer islithographically patterned with light such that the elastomer iscross-linked at discrete sites in the material. These locations are thenable selectively to undergo a shape-change response to an orthogonalstimulus relative to sites that were not radiated with light and thusleft in the non-writeable state, without the cross-links.

In some implementations, the liquid crystal elastomer islithographically patterned with an electric field such that theelastomer is intentionally cross-linked at discrete sites in thematerial. These locations are then able selectively to undergo ashape-change response to an orthogonal stimulus relative to sites thatwere not exposed to an electrical potential and thus left in thenon-writeable state, without the cross-links.

The electrically conductive material can be a functionalized polymer.For example1,4-bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-methylbenzene (RM82) canbe functionalized with methylcoumarin to yieldmethylcoumarin-functionalized RM82, with anthracene to yieldanthracene-functionalized RM82. FIG. 1 is an example reaction of RM82with methylcoumarin to yield methylcoumarin-functionalized RM82.Functionalized RM82 can then be induced into a writeable state by thefirst signal, for example ultraviolet (UV) light with a firstwavelength. In some implementations, exposure to 365 nm light results indimerization of the methylcoumarin moiety, which crosslinks thefunctionalized RM82 into a polymeric network. The polymeric network isthe writeable state for this example. FIG. 2A is an example reaction ofRM82 with methylthioanthracene to yield anthracene-functionalized RM82.Anthracene-functionalized RM82 is also capable of cross-linking inresponse to a first signal, for example UV light with a firstwavelength. In some implementations, anthracene-functionalized RM82 iscrosslinked in response to 365 nm light.

In some implementations, two RM82 moieties can be crosslinked initiallywith 2,2′-(ethylenedioxy)diethanol (EDDET) and capped withmethylthioanthracene. FIG. 2B shows the reaction product of the reactionbetween EDDET, RM82, and methylthioanthracene in a 1:2:2 molar ratio.The inclusion of EDDET can result in a polymer with appropriateelasticity for use in the stimulus-responsive applications described inthis application.

The functionalized RM82 can return to the non-writeable state byexposure to a second signal, for example exposure to UV light with asecond wavelength. In some implementations, the functionalized RM82 canreturn to the non-writeable state in response to a light with awavelength of 254 nm. Exposure to this light causes thefunctionalization reaction to reverse, and the material enters anon-writeable state. In some implementations, the second signal can beheat. For example, when RM82 is functionalized with anthracene, thereversion of the crosslinking reaction can be achieved with heat (above100° C.).

In the polymeric/writeable state, exposure to an orthogonal signalresults in an actuation or a strain. For example, exposure to heat cancause the polymeric network to shift from a nematic, semi-ordered phaseto an isotropic or fluid-like phase. This shift results in an actuationor strain in the polymeric network.

The orthogonal stimulus can be an electric field, a magnetic field,light, heat, or a chemical, metabolite, or both. The orthogonal stimuluscan be a change in an electric field, magnetic field, light, heat, or achange in the concentration of a chemical, metabolite, or both.

In one example, the electrically conductive materials with a writeableand non-writeable state can be used in antennas. The electricallyconductive material in the antenna can be a functionalized polymer. Theantenna can include sensitizers. These antennas can be used to sensechanges in an environment, for example changes in an electric field,magnetic field, light, heat, or the concentration of a chemical,metabolite, or both. If the antennas are exposed to the first signal,the antenna is then “on” or in a writeable state. Subsequent exposure toan orthogonal stimulus can cause the antenna to change shape, forexample unfold, fold, roll, or unroll. In some implementations, thechange in shape changes the polarization handedness or chirality of theantenna. The shape change can then result in the antenna generating asignal. The signal can then be read by a receiver. The crosslinkedfunctionalized liquid crystal elastomer can be configured to reverse thecrosslinking reaction in response to a second signal and thus transitioninto a ‘non-writeable’ state.

The antenna can respond to an orthogonal signal. The orthogonal signalcan be an electric field, a magnetic field, light, heat, or a chemical,metabolite, or both. The orthogonal signal can be a change in anelectric field, magnetic field, light, heat, or a change in theconcentration of a chemical, metabolite, or both. Exposure to anorthogonal signal can cause a shape change in the antenna.

The antenna can be configured to change in polarization or to change inresonance frequency in response to the strain or actuation. In someimplementations, the change in shape changes the polarization handednessor chirality of the antenna. The shape change can then result in theantenna generating a signal. The signal can then be read by a receiver.The crosslinked functionalized liquid crystal elastomer can beconfigured to reverse the crosslinking reaction in response to a secondsignal and thus transition into a ‘non-writeable’ state. In someimplementations, the antenna is produced with liquid crystal elastomersand includes conductive materials, nanomaterials, fibers, or nanofibers.For example, the antenna can include for example carbon black, carbonnanotubes, carbon nanofiber, or carbon fiber. The conductive materials,nanomaterials, fiber and nanofibers improve the electric fieldsensitivity of the antenna. The antenna can be programmed to respond toa first signal, a second signal, and an orthogonal signal. In someimplementations, the antenna can be programmed by varying thecomposition of the liquid crystal elastomer.

The electrically conductive material with a writeable, non-writeable,and stimulated state can be used in a system as a means of generating asignal in response to an orthogonal signal. For example, a system caninclude a functionalized liquid crystal elastomer, a signal generatingelement, and a signal receiving element. The functionalized liquidcrystal elastomer can be functionalized to crosslink in response to afirst signal to generate a crosslinked functionalized liquid crystalelastomer. The crosslinked functionalized liquid crystal elastomer canbe configured to induce a strain in or actuate the signal generatingelement in response to an orthogonal signal. Inducing a strain oractuating the signal generating element can induce the signal generatingelement to generate a readout signal. For example, the signal generatingelement can be an antenna. The antenna can be configured to change inpolarization or to change in resonance frequency in response to thestrain or actuation. The crosslinked functionalized liquid crystalelastomer can be configured to reverse the crosslinking reaction inresponse to a second signal. In some implementations, the first signalis a first light with a first wavelength. In some implementations, thesecond signal is a second light with a second wavelength.

The system can generate a readout signal in response to an orthogonalsignal. The orthogonal signal can be an environmental signal. Theenvironmental signal can be an electric field, a magnetic field, a thirdlight with a third wavelength or the presence of a chemical, metabolite,or both. The environmental signal can be a change in an electric field,magnetic field, a third light with a third wavelength or a change in theconcentration of a chemical, metabolite, or both.

The system can also include a sensitizer. In this instance, a sensitizeris an additive which increases the sensitivity of the material to acertain stimulus. In some implementations, the sensitizer can be anelectric field sensitizer, for example carbon black, carbon nanotubes,carbon nanofiber, or carbon fiber. The sensitizer can be a chromophoricsensitizer, for example titania nanoparticles, n-doped titaniananoparticles, p-doped titania nanoparticles, porphyrins, expandedporphyrins, conjugated porphyrins, polythiophene, polyaniline,polyphenylene, vinylene, rhodamine dye or fluorescein dye.

The functionalized electrically conductive material in the system can befunctionalized RM82. As described herein, the RM82 can be functionalizedwith, for example, methylcoumarin or anthracene.

The system can be used to monitor an environment, for example a wellboreor a subterranean formation. For example, FIG. 3 is an example of amethod 300 for monitoring an environment or formation using afunctionalized liquid crystal elastomer sensor. The method 300 caninclude placing a functionalized liquid crystal elastomer sensor in theenvironment or formation. At 302, the functionalized liquid crystalelastomer sensor is placed in an environment or formation. Thefunctionalized liquid crystal elastomer sensor can include afunctionalized liquid crystal elastomer, and a signal generatingelement. At 304 a first signal is provided to the functionalized liquidcrystal sensor. The first signal can be a first light with a firstwavelength. The functionalized liquid crystal elastomer can beconfigured to respond to the first signal by reacting in a crosslinkingreaction to generate a crosslinked functionalized liquid crystalelastomer. The functionalized liquid crystal elastomer can befunctionalized RM82. In some implementations, the first signal isprovided to the functionalized liquid crystal sensor before placing thesensor in an environment or formation. In some implementations, thefirst signal is provided to the functionalized liquid crystal sensorafter placing the sensor in an environment or formation.

At 306 the sensor is exposed to an orthogonal signal. The orthogonalsignal can be an environmental signal. For example, the environmentalsignal can be an electric field, a magnetic field, a third light with athird wavelength, heat, or the presence of a chemical, metabolite, orboth. The environmental signal can be a change in an electric field, achange in a magnetic field, a change in a third light with a thirdwavelength, a change in heat, or a change in the concentration of achemical, metabolite, or both. The crosslinking functionalized liquidcrystal elastomer can be configured to react in response to theorthogonal signal to induce a strain in or actuate the signal generatingelement. The signal generating element can be configured to generate areadout signal at 308 in response to the strain or actuation. The methodcan include receiving the readout signal with a signal receivingelement.

In some implementations, generating the readout signal includesgenerating the readout signal with an antenna. For example, the strainor actuation in the signal generating element can induce an antenna tochange in polarization or to change in resonance frequency.

The method can include providing a second signal to the sensor. Thecrosslinked functionalized liquid crystal sensor can be configured toreverse the crosslinking reaction in response to the second signal. Thesecond signal can be a second light with a second wavelength.

The method can include placing a liquid crystal sensor that includes asensitizer. The sensitizer can be an electric field sensitizer, forexample carbon black, carbon nanotubes, carbon nanofiber, or carbonfiber. The sensitizer can be a chromophoric sensitizer, for exampletitania nanoparticles, n-doped titania nanoparticles, p-doped titaniananoparticles, porphyrins, expanded porphyrins, conjugated polymers,polythiophene, polyaniline, polyphenylene vinylene, rhodamine dye, orfluorescein dye.

The electrically conductive materials with a writeable, non-writeable,and stimulated state can be used in resistors, capacitors, inductors,interconnects, and field-effect transistors. Interconnects are physicalor logical connections between two electronic devices in a computer ormicrocontroller. The electrically conductive materials described can beused in a semiconductor to dynamically adjust doping content through thereversibly controlled expansion or contraction of the material used asthe semiconductor.

These liquid crystal elastomer (LCE) materials can also be used assensors that are tunable by the dynamic surface area of the dynamicallyaddressable actuating material. LCEs can expand and contract in responseto a temperature transition. These expansions and contractions maycorrespond to variations in surface area.

The electrically conductive material, system, or method can be used indrilling and in subterranean formations. For example, the electricallyconductive material can be used in well completion operations wherereversibly expandable materials are needed. If the electricallyconductive material is responsive to heat as an orthogonal signal, theactuation of the material may be tuned to the dynamic thermalenvironment of the downhole wellbore. Accordingly, drilling equipment,for example a wellbore casing, can respond to the dynamic thermalexpansion and contraction that occurs during production cycling.

The electrically conductive material can be used for other purposes. Forexample, the material can be used in a self-propelling polymer orpolymer composite material, where the propulsion of the material isachieved through the actuation of the material.

EXAMPLES

Dichloromethane, sodium sulfate, mercaptomethylcoumarin, hydrochloricacid, and diazabicyloundec-7-ene (DBU) were obtained from Sigma-Aldrich.The syntheses are presented in the following examples:

Example 1: Preparation of Mercaptomethylcoumarin Functionalized RM82

10.0 g of RM82 and 3.4 g of mercaptomethylcoumarin (Sigma-Aldrich) wereadded to a round bottom flask and dissolved in 100 mL of dichloromethane(Sigma-Aldrich). 1.8 g diazabicyloundec-7-ene (DBU) (Sigma-Aldrich) wasadded with stirring, and the mixture was allowed to stir at roomtemperature overnight. The product was washed with 1 M HCl, 0.1 M HCl,and deionized water, then dried over sodium sulfate (Sigma-Aldrich). Thesolvent was removed with a rotovap to yield the desired product.

Example 2: Preparation of Anthracene Functionalized RM82

EDDET, RM82, and methylthioanthracene were reacted in a 1:2:2 molarratio. To a clean round bottom flask, 0.68 g of EDDET, 1.67 g ofmethylthioanthracene and 2.26 g of triethylamine were dissolved in 30 mLof chloroform with a stir bar. In a separate clean container, 5.0 g ofRM82 were dissolved in 20 mL of chloroform. The RM82 solution was pouredinto the round bottom flask with rapid stirring and covered withaluminium foil. The reaction was allowed to proceed overnight.

After stirring overnight, the mixture was pumped down via rotovap toremove chloroform. The mixture was redissolved in fresh chloroform andwashed with 1 M HCl twice, then saturated NaCl brine twice, thendeionized water once. Sodium sulfate anhydrous was used to removeremaining excess water and the organic phase was collected via a cleanBuchner flask and vacuum filtration. The organic phase was then removedunder vacuum for 2 hours.

Example 3: Preparation of Electrical Field Sensitized LCEs

10 grams of the LCE produced from Example 1 or Example 2 was blendedunder high shear (>500 s⁻¹) with 0.05 grams of multiwall carbonnanotubes to render an electrical field sensitized LCE.

Example 4: Procedure for UV-Crosslinking of Anthracene and CoumarinFunctionalized LCEs

5 grams of the LCE produced in Examples 1, 2, or 3 was placed inside ofa syringe with a 1.0 mm orifice and extruded. Upon extrusion a 365 nmwavelength light radiates the extruding product to cross link thematerial.

Example 5: Procedure for UV-Crosslinking of Anthracene and CoumarinFunctionalized LCEs

0.1 grams of the material produced in Examples 1, 2, or 3 is shearedbetween two quartz plates (dimensions—2 mm×1 cm×4 cm) 365 nm light isapplied through the glass to cross-link the shear-aligned LCE.

Example 6: Procedure for Thermal Actuation

A linear piece of the LCE produced in Examples 4 or 5 is heated througha thermal transition of 20° C. to result in a shape-change and actuationresponse quantified as strain.

The following units of measure have been mentioned in this disclosure:

Unit of Measure Full form ° C. degree Celsius g gram S Siemens m metercm centimeter M molar (moles/liter)

In some implementations, a composition contains an electricallyconductive material. The electrically conductive material can beconfigured to respond to a first signal and enter a writeable state. Theelectrically conductive material can be configured to respond to anorthogonal signal to enter a stimulated state.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The electrically conductive material canbe a functionalized liquid crystal elastomer. The functionalized liquidcrystal elastomer can be configured to generate a crosslink between thefunctionalized liquid crystal elastomers in response to the first signalto generate a crosslinked functionalized liquid crystal elastomer.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The first signal can be alithographically patterned light applied to the functionalized liquidcrystal elastomer to generate crosslinks between the liquid crystalelastomers at discrete sites in the electrically conductive material.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The first signal can be alithographically patterned electric field applied to the functionalizedliquid crystal elastomer to generate crosslinks between the liquidcrystal elastomers at discrete sites in the electrically conductivematerial.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The crosslinked functionalized liquidcrystal elastomer can be configured to respond to the orthogonal signalby changing confirmation or shape.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. Changing conformation or shape of thecrosslinked functionalized liquid crystal elastomer can induce a strainin or actuate the crosslinked functionalized liquid crystal elastomer.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The composition can include a responsematerial. The response material can be configured to propagate a readoutsignal in response to strain or actuation.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The response material can be an antenna.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The antenna can be configured to changein polarization or resonance frequency in response to strain oractuation of the functionalized liquid crystal elastomer.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The crosslinked functionalized liquidcrystal elastomer can be configured to break the crosslink in responseto a second signal to generate the functionalized liquid crystalelastomer.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The first signal can be a first lightwith a first wavelength.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The second signal can be a second lightwith a second wavelength.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The second signal can be heat.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The orthogonal signal can be a firstenvironmental signal.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The first environmental signal can be anelectric field, a magnetic field, or a third light with a thirdwavelength.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The first environmental signal can be achange in an electric field, a change in a magnetic field, a change in alight, a change in heat, or a change in concentration of a chemical,metabolite, or both.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The composition can include asensitizer.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The sensitizer can be an electric fieldsensitizer.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The electric field sensitizer can be atleast one of carbon black, carbon nanotubes, carbon nanofiber, or carbonfiber.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The sensitizer can be a chromophoricsensitizer.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The chromophoric sensitizer can be atleast one of titania nanoparticles, n-doped titania nanoparticles,p-doped titania nanoparticles, porphyrins, expanded porphyrins,conjugated polymers, polythiophene, polyaniline, polyphenylene vinylene,rhodamine dye or fluorescein dye.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The electrically conductive material canbe functionalized RM82.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The functionalized RM82 can befunctionalized with methylcoumarin.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The functionalized RM82 can befunctionalized with anthracene.

In some implementations, a system includes a functionalized liquidcrystal elastomer, a signal generating element, and a signal receivingelement. The functionalized liquid crystal elastomer can befunctionalized to generate a crosslink between functionalized liquidcrystal elastomers in response to a first signal. This generates acrosslinked functionalized liquid crystal elastomer. The crosslinkedfunctionalized liquid crystal elastomer can be configured to induce astrain in or actuate the signal generating element in response to anorthogonal signal. Inducing strain or actuating the signal generatingelement induces the signal generating element to generate a readoutsignal. The signal receiving element can be configured to receive thesignal.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The signal generating element can be anantenna.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The antenna can be configured to changein polarization or in resonance frequency in response to strain oractuation.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The crosslinked functionalized liquidcrystal elastomer is configured to break the crosslink in response to asecond signal.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The first signal can be a first lightwith a first wavelength.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The first signal can be alithographically patterned light applied to the functionalized liquidcrystal elastomer to generate crosslinks between the liquid crystalelastomers at discrete sites.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The first signal can be alithographically patterned electric field applied to the functionalizedliquid crystal elastomer to generate crosslinks between the liquidcrystal elastomers at discrete sites.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The second signal can be a second lightwith a second wavelength.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The second signal can be heat.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The orthogonal signal can be a firstenvironmental signal.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The first environmental signal can be anelectric field, a magnetic field, a third light with a third wavelength,or a chemical, a metabolite, or both.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The first environmental signal can be achange in an electric field, a change in a magnetic field, a change in alight, a change in heat, or a change in concentration of a chemical,metabolite, or both.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The system can include a sensitizer.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The sensitizer can be an electric fieldsensitizer.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The electric field sensitizer can be atleast one of carbon black, carbon nanotubes, carbon nanofiber, or carbonfiber.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The sensitizer can be a chromophoricsensitizer.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The chromophoric sensitizer can be atleast one of titania nanoparticles, n-doped titania nanoparticles,p-doped titania nanoparticles, porphyrins, expanded porphyrins,conjugated porphyrins, polythiophene, polyaniline, polyphenylenevinylene, rhodamine dye or fluorescein dye.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The functionalized liquid crystalelastomer can be functionalized RM82.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The functionalized RM82 can befunctionalized with methylcoumarin.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The functionalized RM82 can befunctionalized with anthracene.

In some implementations, a method for monitoring an environment or aformation includes placing a sensor in the environment or formation. Thesensor can include a functionalized liquid crystal elastomer. The sensorcan include a signal generating element. The method can includeproviding a first signal to the sensor. In response to the first signal,the functionalized liquid crystal elastomer reacts in a crosslinkingreaction to generate a crosslinked functionalized liquid crystalelastomer. The method can include exposing the sensor to an orthogonalsignal. In response to the orthogonal signal, the crosslinkedfunctionalized liquid crystal elastomer can induce a strain in oractuate the signal generating element. Inducing strain in or actuatingthe signal generating element induces the signal generating element togenerate a readout signal.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The first signal can be alithographically patterned light applied to the functionalized liquidcrystal elastomer to generate crosslinks between the liquid crystalelastomers at discrete sites.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The first signal can be alithographically patterned electric field applied to the functionalizedliquid crystal elastomer to generate crosslinks between the liquidcrystal elastomers at discrete sites.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The method can include receiving thesignal with a signal receiving element.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The method can include generating thereadout signal with an antenna.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The method can include generating thesignal by a change in polarization or resonance frequency of theantenna.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The method can include providing asecond signal to the sensor. In response to the second signal thecrosslinking reaction can be reversed.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The method can include providing thefirst signal, wherein the first signal is a first light with a firstwavelength.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The first signal can be a first lightwith a first wavelength.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The second signal can be a second lightwith a second wavelength.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The second signal can be heat.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The orthogonal signal can be anenvironmental signal.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The environmental signal can be anelectric field, a magnetic field, a third light with a third wavelength,heat, or a chemical, metabolite, or both.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The environmental signal can be a changein an electric field, a change in a magnetic field, a change in a thirdlight with a third wavelength, a change in heat or a change inconcentration of a chemical, metabolite, or both.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The sensor can include a sensitizer.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The sensitizer can be an electric fieldsensitizer.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The electric field sensitizer can be atleast one of carbon black, carbon nanotubes, carbon nanofiber, or carbonfiber.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The sensitizer can be a chromophoricsensitizer.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The chromophoric sensitizer can be atleast one of titania nanoparticles, n-doped titania nanoparticles,p-doped titania nanoparticles, porphyrins, expanded porphyrins,conjugated polymers, polythiophene, polyaniline, polyphenylene vinylene,rhodamine dye or fluorescein dye.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The functionalized liquid crystalelastomer can be functionalized RM82.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The functionalized RM82 can befunctionalized with methylcoumarin.

This aspect, taken alone or combinable with any other aspect, caninclude the following features. The functionalized RM82 can befunctionalized with anthracene.

The term “about” as used in this disclosure can allow for a degree ofvariability in a value or range, for example, within 10%, within 5%, orwithin 1% of a stated value or of a stated limit of a range.

The term “electrically conductive material” as used in this disclosurerefers to a material that allows the flow of electric current, forexample a material a material with a conductivity (σ) equal to orgreater than 10 S/m.

The term “elastomer” as used in this disclosure refers to a polymer withelasticity and viscosity.

The term “sensitizer” as used in this disclosure refers to a materialthat enhances the sensitivity or responsiveness, or extends the range ofsensitivity, of an electrically conductive material or a crosslinkedelastomer to an orthogonal signal.

The term “substantially” as used in this disclosure refers to a majorityof, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%,97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more.

The term “solvent” as used in this disclosure refers to a liquid thatcan dissolve a solid, another liquid, or a gas to form a solution.Non-limiting examples of solvents are silicones, organic compounds,water, alcohols, ionic liquids, and supercritical fluids.

The term “room temperature” as used in this disclosure refers to atemperature of about 15 degrees Celsius (° C.) to about 28° C.

The term “downhole” as used in this disclosure refers to under thesurface of the earth, such as a location within or fluidly connected toa wellbore.

As used in this disclosure, the term “subterranean material” or“subterranean zone” refers to any material under the surface of theearth, including under the surface of the bottom of the ocean. Forexample, a subterranean zone or material can be any section of awellbore and any section of a subterranean petroleum—or water-producingformation or region in fluid contact with the wellbore. Placing amaterial in a subterranean zone can include contacting the material withany section of a wellbore or with any subterranean region in fluidcontact the material. Subterranean materials can include any materialsplaced into the wellbore such as cement, drill shafts, liners, tubing,casing, or screens; placing a material in a subterranean zone caninclude contacting with such subterranean materials.

As used in this disclosure, “weight percent” (wt. %) can be considered amass fraction or a mass ratio of a substance to the total mixture orcomposition. Weight percent can be a weight-to-weight ratio ormass-to-mass ratio, unless indicated otherwise.

A number of implementations of the disclosure have been described.Nevertheless, it will be understood that various modifications may bemade without departing from the spirit and scope of the disclosure.

1-19. (canceled)
 20. A method for monitoring an environment orformation, comprising: placing a sensor comprising a functionalizedliquid crystal elastomer in the environment or formation, wherein thesensor comprises a signal generating element; providing a first signalto the sensor, wherein, in response to the first signal thefunctionalized liquid crystal elastomer reacts in a crosslinkingreaction to generate a crosslinked functionalized liquid crystalelastomer; and exposing the sensor to an orthogonal signal, wherein thecrosslinked functionalized liquid crystal elastomer reacts in responseto the orthogonal signal to induce a strain in or actuate the signalgenerating element, and wherein inducing the strain in or actuating thesignal generating element induces the signal generating element togenerate a readout signal.
 21. The method of claim 20, wherein the firstsignal comprises a lithographically patterned light applied to thefunctionalized liquid crystal elastomer to generate crosslinks betweenthe functionalized liquid crystal elastomers at discrete sites.
 22. Themethod of claim 20, wherein the first signal comprises alithographically patterned electric field applied to the functionalizedliquid crystal elastomer to generate crosslinks between thefunctionalized liquid crystal elastomers at discrete sites.
 23. Themethod of claim 20, further comprising receiving the signal with asignal receiving element.
 24. The method of claim 20, wherein generatingthe readout signal comprises generating the readout signal with anantenna.
 25. The method of claim 24, wherein generating the signal withthe antenna further comprises generating the signal by a change inpolarization or resonance frequency of the antenna.
 26. The method ofclaim 20, further comprising providing a second signal to the sensor,wherein in response to the second signal the crosslinking reaction isreversed.
 27. The method of claim 20, wherein providing the first signalfurther comprises providing the first signal wherein the first signal isa first light with a first wavelength.
 28. The method of claim 26,wherein the providing the second signal to the sensor further comprisesproviding the second signal wherein the second signal comprises a secondlight at a second wavelength.
 29. The method of claim 26, whereinproviding the second signal to the sensor further comprises providingthe second signal wherein the second signal is heat.
 30. The method ofclaim 20, wherein exposing the sensor to the orthogonal signal furthercomprises exposing the sensor to an environmental signal.
 31. The methodof claim 30, wherein exposing the sensor to the environmental signalfurther comprises exposing the sensor to an electric field, a magneticfield, a third light with a third wavelength, heat, a chemical, or ametabolite, or any combinations thereof
 32. The method of claim 30,wherein exposing the sensor to the environmental signal furthercomprises exposing the sensor to a change in an electric field, a changein a magnetic field, a change in a third light with a third wavelength,a change in heat, a change in concentration of a chemical, or a changein concentration of a metabolite, or any combinations thereof.
 33. Themethod of claim 20, wherein the functionalized liquid crystal elastomercomprises a functionalized RM82.
 34. The method of claim 33, wherein thefunctionalized RM82 is functionalized with methylcoumarin.
 35. Themethod of claim 33, wherein the functionalized RM82 is functionalizedwith anthracene.